JP4907074B2 - Lubricating oil composition for transmission - Google Patents
Lubricating oil composition for transmission Download PDFInfo
- Publication number
- JP4907074B2 JP4907074B2 JP2004308828A JP2004308828A JP4907074B2 JP 4907074 B2 JP4907074 B2 JP 4907074B2 JP 2004308828 A JP2004308828 A JP 2004308828A JP 2004308828 A JP2004308828 A JP 2004308828A JP 4907074 B2 JP4907074 B2 JP 4907074B2
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- JP
- Japan
- Prior art keywords
- meth
- acrylate
- group
- oil
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 66
- 239000010687 lubricating oil Substances 0.000 title claims description 44
- 230000005540 biological transmission Effects 0.000 title description 50
- 239000002199 base oil Substances 0.000 claims description 67
- 230000001050 lubricating effect Effects 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 229920000193 polymethacrylate Polymers 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 50
- -1 alkylnaphthalenes Chemical class 0.000 description 42
- 239000000178 monomer Substances 0.000 description 29
- 239000003921 oil Substances 0.000 description 23
- 125000000217 alkyl group Chemical group 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- 239000002480 mineral oil Substances 0.000 description 10
- 235000010446 mineral oil Nutrition 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004678 hydrides Chemical class 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 229920013639 polyalphaolefin Polymers 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000994 depressogenic effect Effects 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000376 effect on fatigue Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000006078 metal deactivator Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- 150000005691 triesters Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000003901 ceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012184 mineral wax Substances 0.000 description 2
- 125000002819 montanyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 2
- TYQTYRXEMJXFJG-UHFFFAOYSA-N phosphorothious acid Chemical compound OP(O)S TYQTYRXEMJXFJG-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- MBIZXFATKUQOOA-UHFFFAOYSA-N 1,3,4-thiadiazole Chemical compound C1=NN=CS1 MBIZXFATKUQOOA-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- VRMHHVOBVLFRFB-UHFFFAOYSA-N 2-(2-cyanoethylsulfanylmethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CSCCC#N VRMHHVOBVLFRFB-UHFFFAOYSA-N 0.000 description 1
- LLEFDCACDRGBKD-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;nonanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCCC(O)=O LLEFDCACDRGBKD-UHFFFAOYSA-N 0.000 description 1
- CWTQBXKJKDAOSQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;octanoic acid Chemical compound CCC(CO)(CO)CO.CCCCCCCC(O)=O CWTQBXKJKDAOSQ-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- KYLIZBIRMBGUOP-UHFFFAOYSA-N Anetholtrithion Chemical group C1=CC(OC)=CC=C1C1=CC(=S)SS1 KYLIZBIRMBGUOP-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- DJBVDAUKGXUPLO-QEMDMZNVSA-N C(C)C(C(=O)O)CCCC.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O Chemical compound C(C)C(C(=O)O)CCCC.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O DJBVDAUKGXUPLO-QEMDMZNVSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- URGQBRTWLCYCMR-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] nonanoate Chemical compound CCCCCCCCC(=O)OCC(CO)(CO)CO URGQBRTWLCYCMR-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WDNQRCVBPNOTNV-UHFFFAOYSA-N dinonylnaphthylsulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 WDNQRCVBPNOTNV-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- LZJUZSYHFSVIGJ-UHFFFAOYSA-N ditridecyl hexanedioate Chemical compound CCCCCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCCCCCCC LZJUZSYHFSVIGJ-UHFFFAOYSA-N 0.000 description 1
- FVBSDVQDRFRKRF-UHFFFAOYSA-N ditridecyl pentanedioate Chemical compound CCCCCCCCCCCCCOC(=O)CCCC(=O)OCCCCCCCCCCCCC FVBSDVQDRFRKRF-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002818 heptacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 150000002460 imidazoles Chemical class 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002465 nonacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
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- 229960001860 salicylate Drugs 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Lubricants (AREA)
Description
本発明は変速機用潤滑油組成物に関し、詳しくは低粘度であっても疲労寿命が長い、自動車用の自動変速機、手動変速機、無段変速機に好適な変速機用潤滑油組成物に関する。 TECHNICAL FIELD The present invention relates to a lubricating oil composition for a transmission, and more particularly, a lubricating oil composition for a transmission suitable for an automatic transmission, a manual transmission, and a continuously variable transmission for automobiles having a long fatigue life even though the viscosity is low. About.
近年、炭酸ガス排出量の削減など、環境問題への対応から自動車、建設機械、農業機械等の省エネルギー化、すなわち、省燃費化が急務となっており、エンジンや変速機、終減速機、圧縮機、油圧装置等の装置には省エネルギーへの寄与が強く求められている。そのため、これらに使用される潤滑油には、従来に比べより攪拌抵抗や摩擦抵抗を減少することが求められている。 In recent years, there has been an urgent need to save energy in automobiles, construction machinery, agricultural machinery, etc., that is, to save fuel, in response to environmental issues such as reducing carbon dioxide emissions. Engines, transmissions, final reduction gears, compression Devices such as machines and hydraulic devices are strongly required to contribute to energy saving. Therefore, the lubricating oil used for these is required to reduce the stirring resistance and frictional resistance as compared with the conventional one.
変速機および終減速機の省燃費化手段のひとつとして、潤滑油の低粘度化が挙げられる。例えば、変速機の中でも自動車用自動変速機や無段変速機はトルクコンバータ、湿式クラッチ、歯車軸受機構、オイルポンプ、油圧制御機構などを有し、また、手動変速機や終減速機は歯車軸受機構を有しており、これらに使用される潤滑油をより低粘度化することにより、トルクコンバータ、湿式クラッチ、歯車軸受機構およびオイルポンプ等の攪拌抵抗および摩擦抵抗が低減され、動力の伝達効率が向上することで自動車の燃費の向上が可能となる。 As one of the fuel saving means of the transmission and the final reduction gear, there is a reduction in viscosity of the lubricating oil. For example, among automatic transmissions, automatic transmissions for automobiles and continuously variable transmissions have torque converters, wet clutches, gear bearing mechanisms, oil pumps, hydraulic control mechanisms, etc., and manual transmissions and final reduction gears have gear bearings. By reducing the viscosity of the lubricating oil used in these mechanisms, the stirring resistance and friction resistance of torque converters, wet clutches, gear bearing mechanisms, oil pumps, etc. are reduced, and power transmission efficiency As a result, the fuel efficiency of the automobile can be improved.
しかしながら、これらに使用される潤滑油を低粘度化すると疲労寿命が大幅に低下し、焼付きなどが生じて変速機等に不具合が生じることがある。特に低粘度油の極圧性を向上させるためにリン系極圧剤を配合した場合には、疲労寿命が著しく悪化してしまうため低粘度化することは一般に困難である。また、硫黄系極圧剤は、潤滑油の疲労寿命を改善できるが、一般に低潤滑の条件下においては、添加剤よりも基油粘度の影響が大きいことが知られている。 However, when the viscosity of the lubricating oil used in these is reduced, the fatigue life is significantly reduced, and seizure or the like may occur, resulting in problems with the transmission or the like. In particular, when a phosphorus-based extreme pressure agent is blended in order to improve the extreme pressure property of a low-viscosity oil, it is generally difficult to reduce the viscosity because the fatigue life is remarkably deteriorated. Further, it is known that the sulfur-based extreme pressure agent can improve the fatigue life of the lubricating oil, but generally the influence of the base oil viscosity is larger than that of the additive under the condition of low lubrication.
従来の自動車用変速機油としては、変速特性等の各種性能を長期間維持できるものとして、合成油及び／又は鉱油系の潤滑油基油、摩耗防止剤、極圧剤、金属系清浄剤、無灰分散剤、摩擦調整剤、粘度指数向上剤等を最適化して配合したものが報告されている（例えば、特許文献１〜４参照。）。しかしながら、これらの組成物はいずれも燃費向上を目的としたものではないためその動粘度は高く、潤滑油を低粘度化した場合の疲労寿命への影響については全く検討されておらず、従ってそのような課題を解決しうる組成物についてはこれまでに十分検討されていない。
本発明はこのような実情に鑑みなされたものであり、その目的は、低粘度であっても疲労寿命が長い、変速機用潤滑油組成物、特に自動車用の自動変速機、手動変速機、無段変速機等に好適な、省燃費性能と歯車や軸受け等の十分な耐久性を兼ね備えた潤滑油組成物を提供することにある。 The present invention has been made in view of such circumstances, and its purpose is to provide a lubricating oil composition for a transmission that has a low fatigue life and a long fatigue life, particularly an automatic transmission for an automobile, a manual transmission, An object of the present invention is to provide a lubricating oil composition suitable for a continuously variable transmission or the like, which has both fuel saving performance and sufficient durability such as gears and bearings.
本発明者らは上記課題を解決するために、潤滑油基油とポリマーに着目し、検討した結果、特定の基油と特定のポリ（メタ）クリレート系添加剤を選択して低粘度にした変速機用潤滑油組成物が、上記課題を解決できる事を見いだし、本発明を完成するに至った。 In order to solve the above-mentioned problems, the present inventors paid attention to a lubricating base oil and a polymer, and as a result of examination, selected a specific base oil and a specific poly (meth) acrylate-based additive to reduce the viscosity. The present inventors have found that a transmission lubricating oil composition can solve the above-mentioned problems, and have completed the present invention.
すなわち、本発明は、（Ａ）１００℃における動粘度が１．５〜４．５ｍｍ２／ｓに調整してなる潤滑油基油であって、前記（Ａ）成分が、１００℃における動粘度が１５〜５０ｍｍ２／ｓの潤滑油基油を基油全量基準で３〜３０質量％含む潤滑油基油に（Ｂ）下記一般式（１）で表される構造単位を有し、かつ重量平均分子量が１．５〜３万であるポリ（メタ）アクリレート系添加剤を含有し、組成物の１００℃における動粘度が３〜８ｍｍ２／ｓ、かつ粘度指数が９５〜２００であることを特徴とする変速機用潤滑油組成物にある。
That is, the present invention is (A) a lubricating base oil having a kinematic viscosity at 100 ° C. adjusted to 1.5 to 4.5 mm 2 / s, wherein the component (A) has a kinematic viscosity at 100 ° C. Has a structural unit represented by the following general formula (1) in a lubricating base oil containing 3 to 30% by mass of a lubricating base oil of 15 to 50 mm 2 / s based on the total amount of the base oil, and weight A poly (meth) acrylate-based additive having an average molecular weight of 1.5 to 30,000, a kinematic viscosity at 100 ° C. of the composition of 3 to 8 mm 2 / s, and a viscosity index of 95 to 200 The lubricating oil composition for a transmission is characterized.
以下、本発明を説明する。
本発明における（Ａ）潤滑油基油は、１００℃における動粘度が１．５〜４．５ｍｍ２／ｓに調整してなる潤滑油基油であり、鉱油系潤滑油基油、合成系潤滑油基油及びこれらの混合物を用いることができる。
The present invention will be described below.
(A) Lubricating base oil in the present invention is a lubricating base oil whose kinematic viscosity at 100 ° C. is adjusted to 1.5 to 4.5 mm 2 / s. Mineral oil base oil, synthetic base oil Oil base oils and mixtures thereof can be used.
鉱油系潤滑油基油としては、原油を常圧蒸留及び減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製、硫酸洗浄、白土処理等の精製処理を単独又は二つ以上適宜組み合わせて精製したパラフィン系、ナフテン系等の鉱油系潤滑油基油や、ノルマルパラフィン、イソパラフィン等が挙げられる。なお、これらの基油は単独でも、２種以上任意の割合で組み合わせて使用してもよい。 As a mineral oil base oil, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining. In addition, paraffinic and naphthenic mineral oil base oils, normal paraffins, isoparaffins, and the like, which are refined alone or in appropriate combination of two or more purification treatments such as sulfuric acid washing and clay treatment, can be mentioned. These base oils may be used alone or in combination of two or more at any ratio.
好ましい鉱油系潤滑油基油としては以下の基油を挙げることができる。
(1) パラフィン基系原油および／または混合基系原油の常圧蒸留による留出油；
(2) パラフィン基系原油および／または混合基系原油の常圧蒸留残渣油の減圧蒸留留出油（ＷＶＧＯ）；
(3) 潤滑油脱ろう工程により得られるワックスおよび／またはＧＴＬプロセス等により製造されるフィッシャートロプシュワックス；
(4) (1)〜(3)の中から選ばれる１種または２種以上の混合油のマイルドハイドロクラッキング処理油（ＭＨＣ）；
(5) (1)〜(4)の中から選ばれる２種以上の油の混合油；
(6) (1)、(2)、(3)、(4)または(5)の脱れき油（ＤＡＯ）；
(7) (6)のマイルドハイドロクラッキング処理油（ＭＨＣ）；
(8) (1)〜(7)の中から選ばれる２種以上の油の混合油などを原料油とし、この原料油および／またはこの原料油から回収された潤滑油留分を、通常の精製方法によって精製し、潤滑油留分を回収することによって得られる潤滑油
Preferred mineral oil base oils include the following base oils.
(1) Distilled oil obtained by atmospheric distillation of paraffin-based crude oil and / or mixed-base crude oil;
(2) Vacuum distillation distillate (WVGO) of paraffin-based crude oil and / or mixed-base crude oil at atmospheric distillation residue;
(3) Wax obtained by a lubricant dewaxing step and / or a Fischer-Tropsch wax produced by a GTL process or the like;
(4) Mild hydrocracking treatment oil (MHC) of one or two or more mixed oils selected from (1) to (3);
(5) A mixed oil of two or more oils selected from (1) to (4);
(6) Dried oil (DAO) of (1), (2), (3), (4) or (5);
(7) Mild hydrocracking treatment oil (MHC) of (6);
(8) A mixed oil of two or more kinds of oils selected from (1) to (7) is used as a feedstock oil, and this feedstock oil and / or a lubricating oil fraction recovered from this feedstock oil is used as a normal oil fraction. Lubricating oil obtained by refining by the refining method and collecting the lubricating oil fraction
ここでいう通常の精製方法とは特に制限されるものではなく、潤滑油基油製造の際に用いられる精製方法を任意に採用することができる。通常の精製方法としては、例えば、（ア）水素化分解、水素化仕上げなどの水素化精製、（イ）フルフラール溶剤抽出などの溶剤精製、（ウ）溶剤脱ろうや接触脱ろうなどの脱ろう、（エ）酸性白土や活性白土などによる白土精製、（オ）硫酸洗浄、苛性ソーダ洗浄などの薬品（酸またはアルカリ）精製などが挙げられる。本発明ではこれらの１つまたは２つ以上を任意の組み合わせおよび任意の順序で採用することができる。 The normal refining method here is not particularly limited, and a refining method used in the production of the lubricating base oil can be arbitrarily employed. Examples of conventional purification methods include (a) hydrorefining such as hydrocracking and hydrofinishing, (b) solvent purification such as furfural solvent extraction, and (c) dewaxing such as solvent dewaxing and catalytic dewaxing. And (d) white clay refining with acid clay and activated clay, and (e) chemical (acid or alkali) purification such as sulfuric acid washing and caustic soda washing. In the present invention, one or more of these can be used in any combination and in any order.
本発明で用いる鉱油系潤滑油基油としては、上記(1)〜(8)から選ばれる基油をさらに以下の処理を行って得られる基油が特に好ましい。
すなわち、上記(1)〜(8)から選ばれる基油をそのまま、またはこの基油から回収された潤滑油留分を、水素化分解あるいはワックス異性化し、当該生成物をそのまま、もしくはこれから潤滑油留分を回収し、次に溶剤脱ろうや接触脱ろうなどの脱ろう処理を行い、その後、溶剤精製処理するか、または、溶剤精製処理した後、溶剤脱ろうや接触脱ろうなどの脱ろう処理を行って製造される水素化分解鉱油及び／又はワックス異性化イソパラフィン系基油が好ましく用いられる。この水素化分解鉱油及び／又はワックス異性化イソパラフィン系基油は、基油全量基準で好ましくは３０質量％以上、より好ましくは５０質量％以上、特に好ましくは７０質量％以上使用することが望ましい。
The mineral oil base oil used in the present invention is particularly preferably a base oil obtained by further subjecting the base oil selected from the above (1) to (8) to the following treatment.
That is, the base oil selected from the above (1) to (8) is used as it is, or the lubricating oil fraction recovered from this base oil is hydrocracked or wax isomerized, and the product is used as it is or from now on. Collect the fraction, and then perform dewaxing treatment such as solvent dewaxing or contact dewaxing, and then solvent refining treatment, or after solvent refining treatment, dewaxing such as solvent dewaxing or contact dewaxing Hydrocracked mineral oil and / or wax isomerized isoparaffinic base oil produced by treatment is preferably used. The hydrocracked mineral oil and / or wax isomerized isoparaffin base oil is preferably used in an amount of 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 70% by mass or more based on the total amount of the base oil.
また、合成系潤滑油基油を例示すれば、ポリα−オレフィン又はその水素化物、イソブテンオリゴマー又はその水素化物、イソパラフィン、アルキルベンゼン、アルキルナフタレン、ジエステル（例えば、ジトリデシルグルタレート、ジ−２−エチルヘキシルアジペート、ジイソデシルアジペート、ジトリデシルアジペート、ジ−２−エチルヘキシルセバケート等）、ポリオールエステル（例えば、トリメチロールプロパンカプリレート、トリメチロールプロパンペラルゴネート、ペンタエリスリトール２−エチルヘキサノエート、ペンタエリスリトールペラルゴネート等）、ポリオキシアルキレングリコール、ジアルキルジフェニルエーテル、ポリフェニルエーテル等が挙げられる。 Examples of synthetic lubricating base oils include poly α-olefins or hydrides thereof, isobutene oligomers or hydrides thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, diesters (eg, ditridecylglutarate, di-2-ethylhexyl). Adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc., polyol esters (eg, trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, etc.) ), Polyoxyalkylene glycol, dialkyl diphenyl ether, polyphenyl ether and the like.
好ましい合成系潤滑油基油としてはポリα−オレフィンが挙げられる。ポリα−オレフィンとしては、典型的には、炭素数２〜３２、好ましくは６〜１６のα−オレフィンのオリゴマーまたはコオリゴマー（例えば、１−オクテンオリゴマー、１−デセンオリゴマー、エチレン−プロピレンコオリゴマー等）及びその水素化物が挙げられる。 Preferable synthetic lubricating base oils include poly α-olefins. The poly α-olefin is typically an α-olefin oligomer or co-oligomer having 2 to 32 carbon atoms, preferably 6 to 16 (eg, 1-octene oligomer, 1-decene oligomer, ethylene-propylene co-oligomer). And hydrides thereof.
ポリα−オレフィンの製法については特に制限はないが、例えば、三塩化アルミニウム、三フッ化ホウ素または三フッ化ホウ素と水、アルコール（例えば、エタノール、プロパノールまたはブタノール）、カルボン酸、またはエステル（例えば、酢酸エチルまたはプロピオン酸エチル）との錯体を含むフリーデル・クラフツ触媒のような重合触媒の存在下でのα−オレフィンの重合等が挙げられる。 There are no particular restrictions on the production method of the poly-α-olefin, but for example, aluminum trichloride, boron trifluoride or boron trifluoride and water, alcohol (for example, ethanol, propanol or butanol), carboxylic acid, or ester (for example, , Polymerization of α-olefin in the presence of a polymerization catalyst such as a Friedel-Crafts catalyst containing a complex with ethyl acetate or ethyl propionate).
本発明における（Ａ）潤滑油基油は、上記のような２種類以上の鉱油系基油同志あるいは合成油系基油同志の混合物であっても差し支えなく、鉱油系基油と合成油系基油との混合物であっても差し支えない。そして、上記混合物における２種類以上の基油の混合比は、任意に選ぶことができる。 The (A) lubricating base oil in the present invention may be a mixture of two or more mineral base oils or synthetic base oils as described above. It can be a mixture with oil. And the mixing ratio of 2 or more types of base oil in the said mixture can be chosen arbitrarily.
本発明の変速機用潤滑油組成物における（Ａ）潤滑油基油は、１００℃における動粘度が１．５〜４．５ｍｍ２／ｓに調整してなる潤滑油基油であり、好ましくは下記（Ａ１）成分、又は（Ａ１）成分と（Ａ２）成分から構成される。
（Ａ１）成分としては、具体的には以下の（Ａ１ａ）〜（Ａ１ｃ）から選ばれる１種又は２種以上を混合して用いることが好ましい。
（Ａ１ａ）１００℃における動粘度が１．５〜３．５ｍｍ２／ｓ未満、好ましくは１．９〜３．２ｍｍ２／ｓの鉱油系基油
（Ａ１ｂ）１００℃における動粘度が３．５〜７ｍｍ２／ｓ未満、好ましくは３．８〜４．５ｍｍ２／ｓの鉱油系基油
（Ａ１ｃ）１００℃における動粘度が１．５〜７ｍｍ２／ｓ未満、好ましくは３．８〜４．５ｍｍ２／ｓのポリα−オレフィン系基油
The (A) lubricating base oil in the lubricating oil composition for transmission of the present invention is a lubricating base oil whose kinematic viscosity at 100 ° C. is adjusted to 1.5 to 4.5 mm 2 / s, preferably It is comprised from the following (A1) component or (A1) component and (A2) component.
As the component (A1), specifically, one or more selected from the following (A1a) to (A1c) are preferably mixed and used.
(A1a) Mineral oil base oil having a kinematic viscosity at 100 ° C. of less than 1.5 to 3.5 mm 2 / s, preferably 1.9 to 3.2 mm 2 / s (A1b) A kinematic viscosity at 100 ° C. of 3.5 ~7mm less than 2 / s, preferably mineral base oils 3.8~4.5mm 2 / s (A1c) a kinematic viscosity at 100 ° C. is 1.5~7mm less than 2 / s, preferably 3.8 to 4 .5 mm 2 / s poly α-olefin base oil
ここで、（Ａ１ａ）〜（Ａ１ｃ）の潤滑油基油の％ＣＡとしては、特に制限はないが、３以下であることが好ましく、２以下であることがさらに好ましく、１以下であることが特に好ましい。（Ａ）潤滑油基油の％ＣＡを３以下とすることでより酸化安定性に優れた組成物を得ることができる。
なお、本発明において％ＣＡとは、ＡＳＴＭ Ｄ ３２３８−８５に準拠した方法により求められる芳香族炭素数の全炭素数に対する百分率を示す。
Here, it as a% C A of the lubricating base oil of (A1a) ~ (A1c), is not particularly limited, preferably 3 or less, more preferably 2 or less, 1 or less Is particularly preferred. (A) a% C A of the lubricating base oil can be obtained more excellent oxidation stability composition by 3 or less.
Note that the% C A in the present invention, showing the percentage of aromatic carbon atoms in total number of carbon obtained by a method in accordance with ASTM D 3238-85.
また、（Ａ１ａ）〜（Ａ１ｃ）の潤滑油基油は、その粘度指数に格別の限定はないが、粘度指数は８０以上が好ましく、より好ましくは９０以上、特に好ましくは１１０以上であり、通常２００以下、好ましくは１６０以下であることが望ましい。粘度指数を８０以上とすることによって、低温から高温にわたり良好な粘度特性を示す組成物を得ることができ、粘度指数が高すぎると疲労寿命に対して効果が小さい。 The lubricating base oils of (A1a) to (A1c) are not particularly limited in their viscosity index, but the viscosity index is preferably 80 or more, more preferably 90 or more, and particularly preferably 110 or more. It is desirable that it is 200 or less, preferably 160 or less. By setting the viscosity index to 80 or more, a composition showing good viscosity characteristics from low temperature to high temperature can be obtained. If the viscosity index is too high, the effect on fatigue life is small.
また、本発明における（Ａ１ａ）〜（Ａ１ｃ）の潤滑油基油は、その硫黄含有量に格別の限定はないが、０．０５質量％以下であることが好ましく、０．０２質量％以下であることがさらに好ましく、０．００５質量％以下であることが特に好ましい。（Ａ）成分の硫黄含有量を低減することで組成物の酸化安定性により優れた組成物を得ることができる。 Further, the lubricating base oils (A1a) to (A1c) in the present invention are not particularly limited in the sulfur content, but are preferably 0.05% by mass or less, and 0.02% by mass or less. More preferably, it is particularly preferably 0.005% by mass or less. By reducing the sulfur content of the component (A), it is possible to obtain a composition that is more excellent in oxidative stability of the composition.
本発明においては、上記（Ａ１ａ）〜（Ａ１ｃ）をそれぞれ単独でも使用することができるが、任意に混合使用することができる。中でも、（Ａ１ａ）と、（Ａ１ｂ）及び／又は（Ａ１ｃ）を併用することが好ましい。なお、（Ａ１ａ）成分及び／又は（Ａ１ｂ）成分と（Ａ１ｃ）成分を併用する場合の（Ａ１ｃ）成分の含有量は、基油全量基準で、好ましくは１〜５０質量％、より好ましくは３〜２０質量％、さらに好ましくは３〜１０質量％である。特に、下記（Ａ２）成分と併用する場合に、（Ａ１ｃ）成分を３〜８質量％程度配合することで、安価かつ効果的に、疲労寿命、低温特性、酸化安定性に優れた効果を発現することができる。 In the present invention, each of the above (A1a) to (A1c) can be used alone, but can be arbitrarily mixed and used. Especially, it is preferable to use together (A1a) and (A1b) and / or (A1c). The content of the component (A1c) when the component (A1a) and / or the component (A1b) and the component (A1c) are used in combination is preferably 1 to 50% by mass, more preferably 3 based on the total amount of the base oil. -20% by mass, more preferably 3-10% by mass. In particular, when used in combination with the following component (A2), by blending the component (A1c) at about 3 to 8% by mass, an effect excellent in fatigue life, low-temperature characteristics, and oxidation stability is exhibited inexpensively and effectively. can do.
本発明の変速機用潤滑油組成物における（Ａ）潤滑油基油としては、疲労寿命を向上させるために、上記（Ａ１）に、さらに（Ａ２）１００℃における動粘度が７〜５０ｍｍ２／ｓの潤滑油基油を用いることが好ましい。
（Ａ２）成分としては、具体的には以下の（Ａ２ａ）〜（Ａ２ｃ）から選ばれる１種又は２種以上を混合して用いることが好ましい。
（Ａ２ａ）１００℃における動粘度が７〜１５ｍｍ２／ｓ未満、好ましくは８〜１２ｍｍ２／ｓの鉱油系及び／又は合成系基油、好ましくは鉱油系基油
（Ａ２ｂ）１００℃における動粘度が１５〜２５ｍｍ２／ｓ未満、好ましくは１７〜２３ｍｍ２／ｓの鉱油系及び／又は合成系基油、好ましくは鉱油系基油
（Ａ２ｃ）１００℃における動粘度が２５〜５０ｍｍ２／ｓ、好ましくは２８〜４０ｍｍ２／ｓの鉱油系及び／又は合成系基油、好ましくは鉱油系基油
In order to improve the fatigue life, (A) the lubricating base oil in the lubricating oil composition for transmission of the present invention has (A2) a kinematic viscosity at 100 ° C. of 7 to 50 mm 2 / It is preferable to use s lubricating base oil.
As the component (A2), specifically, it is preferable to use a mixture of one or more selected from the following (A2a) to (A2c).
(A2a) 100 ° C. is 7~15mm less than 2 / s kinematic viscosity at, preferably mineral and / or synthetic base oils 8 to 12 mm 2 / s, preferably a kinematic viscosity at mineral base oil (A2b) 100 ° C. There 15~25mm less than 2 / s, preferably mineral and / or synthetic base oils 17~23mm 2 / s, preferably a kinematic viscosity at mineral base oil (A2c) 100 ℃ 25~50mm 2 / s, Preferably 28-40 mm 2 / s mineral and / or synthetic base oil, preferably mineral oil base oil
ここで、（Ａ２ａ）〜（Ａ２ｃ）の潤滑油基油の％ＣＡとしては、通常０〜４０であり、特に制限はないが、２以上であることが好ましく、５以上であることがさらに好ましく、８以上であることが特に好ましく、また１５以下であることが好ましく、より好ましくは１０以下であることが、疲労寿命と酸化安定性を両立できる点で望ましい。 Here, the% C A of the lubricating base oil (A2a) ~ (A2c), is usually 0 to 40, in particular, without limitation, is preferably 2 or more, further to be 5 or more It is preferably 8 or more, particularly preferably 15 or less, and more preferably 10 or less, from the viewpoint that both fatigue life and oxidation stability can be achieved.
また、（Ａ２ａ）〜（Ａ２ｃ）の潤滑油基油は、その粘度指数に格別の限定はないが、粘度指数は８０以上が好ましく、より好ましくは９０以上、特に好ましくは９５以上であり、通常２００以下、好ましくは１２０以下、より好ましくは１１０以下、特に好ましくは１００以下であることが望ましい。粘度指数を８０以上とすることによって、低温から高温にわたり良好な粘度特性を示す組成物を得ることができ、粘度指数が高すぎると疲労寿命に対して効果が小さい。 The lubricating base oils (A2a) to (A2c) are not particularly limited in their viscosity index, but the viscosity index is preferably 80 or more, more preferably 90 or more, and particularly preferably 95 or more. It is desirable that it is 200 or less, preferably 120 or less, more preferably 110 or less, and particularly preferably 100 or less. By setting the viscosity index to 80 or more, a composition showing good viscosity characteristics from low temperature to high temperature can be obtained. If the viscosity index is too high, the effect on fatigue life is small.
また、本発明における（Ａ２ａ）〜（Ａ２ｃ）の潤滑油基油は、その硫黄含有量に格別の限定はないが、通常０〜２質量％であり、好ましくは０．０５〜１．５質量％、より好ましくは０．３〜１．２質量％、さらに好ましくは０．５〜１質量％、特に好ましくは０．７〜１質量％であることが望ましい。（Ａ２）成分として硫黄分含有量が比較的高いものを使用することで、疲労寿命を高めることができ、好ましくは１質量％以下のものを使用することで組成物の酸化安定性により優れた組成物を得ることができる。 The lubricating base oils (A2a) to (A2c) in the present invention are not particularly limited in their sulfur content, but are usually 0 to 2% by mass, preferably 0.05 to 1.5% by mass. %, More preferably 0.3 to 1.2% by mass, still more preferably 0.5 to 1% by mass, and particularly preferably 0.7 to 1% by mass. (A2) By using a component having a relatively high sulfur content as the component, the fatigue life can be increased, and preferably by using the component having a content of 1% by mass or less, the oxidation stability of the composition is more excellent. A composition can be obtained.
本発明において（Ａ２）成分を使用する場合、（Ａ２ｂ）又は（Ａ２ｃ）を用いることが疲労寿命向上の点で好ましく、特に（Ａ２ｂ）を用いることが疲労寿命と酸化安定性を両立できる点から好ましい。また、（Ａ１）成分として、（Ａ１ｃ）を用いることで、疲労寿命と酸化安定性及び低温粘度特性に優れた組成物を得ることができる。 In the present invention, when the component (A2) is used, it is preferable to use (A2b) or (A2c) in terms of improving the fatigue life, and in particular, using (A2b) can achieve both fatigue life and oxidation stability. preferable. In addition, by using (A1c) as the component (A1), a composition excellent in fatigue life, oxidation stability, and low-temperature viscosity characteristics can be obtained.
本発明の（Ａ）成分において上記（Ａ１）及び（Ａ２）成分を併用する場合の配合量は、特に制限はないが、潤滑油基油全量基準で、（Ａ１）成分を好ましくは７０〜９７質量％、より好ましくは８５〜９５質量％であり、（Ａ２）成分を好ましくは３〜３０質量％、より好ましくは５〜１５質量％である。 In the component (A) of the present invention, the blending amount when the components (A1) and (A2) are used in combination is not particularly limited, but the component (A1) is preferably 70 to 97 based on the total amount of the lubricating base oil. It is 85 mass%, More preferably, it is 85-95 mass%, (A2) Preferably it is 3-30 mass%, More preferably, it is 5-15 mass%.
本発明における（Ａ）潤滑油基油は上記のように（Ａ１）成分、又は（Ａ１）成分及び（Ａ２）成分からなる潤滑油基油であるが、その１００℃における動粘度は１．５〜４．５ｍｍ２／ｓであり、好ましくは２．８〜４．０ｍｍ２／ｓ、特に好ましくは３．６〜３．９ｍｍ２／ｓである。１００℃における動粘度を４．５ｍｍ２／ｓ以下とすることによって、流体抵抗が小さくなるため潤滑箇所での摩擦抵抗がより小さい潤滑油組成物を得ることが可能となり、低温粘度に優れた組成物（例えば、−４０℃におけるブルックフィールド粘度が２万ｍＰａ・ｓ以下）とすることができる。また、１００℃における動粘度を１．５ｍｍ２／ｓ以上とすることによって、油膜形成が十分となり、潤滑性により優れ、また、高温条件下での基油の蒸発損失がより小さい潤滑油組成物を得ることが可能となる。 The (A) lubricating base oil in the present invention is a lubricating base oil composed of the component (A1) or the components (A1) and (A2) as described above, and the kinematic viscosity at 100 ° C. is 1.5. It is -4.5mm < 2 > / s, Preferably it is 2.8-4.0mm < 2 > / s, Especially preferably, it is 3.6-3.9mm < 2 > / s. By setting the kinematic viscosity at 100 ° C. to 4.5 mm 2 / s or less, it is possible to obtain a lubricating oil composition having a lower frictional resistance at a lubricating location because the fluid resistance becomes smaller, and a composition having excellent low-temperature viscosity. (For example, the Brookfield viscosity at −40 ° C. is 20,000 mPa · s or less). Further, by setting the kinematic viscosity at 100 ° C. to 1.5 mm 2 / s or more, the oil film formation is sufficient, the lubricity is excellent, and the lubricating oil composition has a smaller evaporation loss of the base oil under high temperature conditions. Can be obtained.
また、本発明における（Ａ）潤滑油基油の％ＣＡとしては、特に制限はないが、３以下であることが好ましく、２以下であることがさらに好ましく、１以下であることが特に好ましい。（Ａ）潤滑油基油の％ＣＡを３以下とすることでより酸化安定性に優れた組成物を得ることができる。 As the% C A of (A) a lubricating base oil in the present invention is not particularly limited, preferably 3 or less, more preferably 2 or less, particularly preferably 1 or less . (A) a% C A of the lubricating base oil can be obtained more excellent oxidation stability composition by 3 or less.
また、本発明における（Ａ）潤滑油基油は、その粘度指数に格別の限定はないが、粘度指数は８０以上が好ましく、より好ましくは９０以上、特に好ましくは１１０以上であることが望ましい。粘度指数を８０以上とすることによって、低温から高温にわたり良好な粘度特性を示す組成物を得ることができる。 In addition, the viscosity index of the (A) lubricating base oil in the present invention is not particularly limited, but the viscosity index is preferably 80 or more, more preferably 90 or more, and particularly preferably 110 or more. By setting the viscosity index to 80 or more, it is possible to obtain a composition exhibiting good viscosity characteristics from a low temperature to a high temperature.
また、本発明における（Ａ）潤滑油基油は、その硫黄含有量に格別の限定はないが、好ましくは０〜０．３質量％、より好ましくは０．０３〜０．２質量％、特に好ましくは０．０６〜０．１質量％である。（Ａ）成分の硫黄含有量を上記範囲、特に０．０３〜０．２質量％とすることで、疲労寿命と酸化安定性を両立することができる。 Further, the (A) lubricating base oil in the present invention is not particularly limited in its sulfur content, but is preferably 0 to 0.3% by mass, more preferably 0.03 to 0.2% by mass, particularly Preferably it is 0.06-0.1 mass%. (A) By making sulfur content of a component into the said range, especially 0.03-0.2 mass%, fatigue life and oxidation stability can be made compatible.
本発明の変速機用潤滑油組成物における（Ｂ）成分は、下記一般式（１）で表される構造単位を有するポリ（メタ）アクリレート系添加剤であり、極性基を有しない非分散型ポリ（メタ）クリレート系添加剤であっても、極性基を有する分散型ポリ（メタ）クリレート系添加剤であってもよい。 The component (B) in the lubricating oil composition for transmission of the present invention is a poly (meth) acrylate-based additive having a structural unit represented by the following general formula (1), and has no polar group. Even if it is a poly (meth) acrylate type additive, the dispersion type poly (meth) acrylate type additive which has a polar group may be sufficient.
一般式（１）において、Ｒ１は水素又はメチル基、好ましくはメチル基を示し、Ｒ２は炭素数１６〜３０の直鎖又は分枝状の炭化水素基、好ましくは炭素数２０以上の分枝状炭化水素基を示す。 In the general formula (1), R 1 represents hydrogen or a methyl group, preferably a methyl group, and R 2 represents a straight chain or branched hydrocarbon group having 16 to 30 carbon atoms, preferably a group having 20 or more carbon atoms. A branched hydrocarbon group is shown.
ここで、炭素数１６〜３０の直鎖又は分枝状の炭化水素基としては、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基、ヘキサコシル基、ヘプタコシル基、オクタコシル基、ノナコシル基、トリアコンチル基等のアルキル基（これらアルキル基は直鎖状でも分枝状でもよい）；ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、ノナデセニル基、イコセニル基、ヘンイコセニル基、ドコセニル基、トリコセニル基、テトラコセニル基、ペンタコセニル基、ヘキサコセニル基、ヘプタコセニル基、オクタコセニル基、ノナコセニル基、トリアコンテニル基等のアルケニル基（これらアルケニル基は直鎖状でも分枝状でもよく、また二重結合の位置も任意である）；等及びこれらにが例示できる。 Here, as a C16-30 linear or branched hydrocarbon group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henecosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group Group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, etc. (these alkyl groups may be linear or branched); hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group Alkenyl groups such as henicosenyl group, dococenyl group, tricocenyl group, tetracocenyl group, pentacocenyl group, hexacocenyl group, heptacocenyl group, octacocenyl group, nonacosenyl group and triaconenyl group (these alkenyl groups may be linear or branched) , The position of the double bond is also arbitrary); and the like, and these can be exemplified.
本発明の（Ｂ）成分を構成する一般式（１）で表される構造単位を有するポリ（メタ）アクリレートとしては、下記一般式（１’）で示されるモノマーの１種または２種以上を重合または共重合して得られるポリ（メタ）アクリレートであっても、一般式（１’）で表されるモノマーの１種又は２種以上のモノマーと、一般式（１’）で表されるモノマー以外のモノマーとの共重合体であっても良い。
ＣＨ２＝ＣＨ（Ｒ１）−Ｃ（＝Ｏ）−ＯＲ２ （１’）
（一般式（１’）中におけるＲ１およびＲ２は、一般式（１）のＲ１およびＲ２と同じである。）
As the poly (meth) acrylate having the structural unit represented by the general formula (1) constituting the component (B) of the present invention, one or more of the monomers represented by the following general formula (1 ′) are used. Even a poly (meth) acrylate obtained by polymerization or copolymerization is represented by one or more monomers represented by the general formula (1 ′) and the general formula (1 ′). It may be a copolymer with a monomer other than the monomer.
CH 2 = CH (R 1) -C (= O) -OR 2 (1 ')
(R 1 and R 2 in the general formula (1 ') is the same as R 1 and R 2 in the general formula (1).)
一般式（１’）で示されるモノマーとしては、下記（Ｂ１）及び（Ｂ２）から選ばれる１種又は２種以上のモノマーであることが好ましい。
（Ｂ１）炭素数１６〜３０の直鎖アルキル基を有する（メタ）アクリレート：
（Ｂ１）成分としては、好ましくは炭素数１６〜２０の直鎖アルキル基、より好ましくは炭素数１６又は１８の直鎖アルキル基を有する（メタ）アクリレートであり、具体的には、ｎ−ヘキサデシル（メタ）アクリレート、ｎ−オクタデシル（メタ）アクリレート、ｎ−イコシル（メタ）アクリレート、ｎ−ドコシル（メタ）アクリレート、ｎ−テトラコシル（メタ）アクリレート、ｎ−ヘキサコシル（メタ）アクリレート、ｎ−オクタコシル（メタ）アクリレート等が挙げられ、特にｎ−ヘキサデシル（メタ）アクリレート、ｎ−オクタデシル（メタ）アクリレートが好ましい。
The monomer represented by the general formula (1 ′) is preferably one or more monomers selected from the following (B1) and (B2).
(B1) (Meth) acrylate having a straight chain alkyl group having 16 to 30 carbon atoms:
The component (B1) is preferably a (meth) acrylate having a linear alkyl group having 16 to 20 carbon atoms, more preferably a linear alkyl group having 16 or 18 carbon atoms, and specifically, n-hexadecyl. (Meth) acrylate, n-octadecyl (meth) acrylate, n-icosyl (meth) acrylate, n-docosyl (meth) acrylate, n-tetracosyl (meth) acrylate, n-hexacosyl (meth) acrylate, n-octacosyl (meta) ) Acrylate and the like, and n-hexadecyl (meth) acrylate and n-octadecyl (meth) acrylate are particularly preferable.
（Ｂ２）炭素数１６〜３０の分枝状アルキル基を有する（メタ）アクリレート：
（Ｂ２）成分としては、例えば、分枝ヘキサデシル（メタ）アクリレート、分枝オクタデシル（メタ）アクリレート、分枝イコシル（メタ）アクリレート、分枝ドコシル（メタ）アクリレート、分枝テトラコシル（メタ）アクリレート、分枝ヘキサコシル（メタ）アクリレート、分枝オクタコシル（メタ）アクリレート等が挙げられ、好ましくは−Ｃ−Ｃ（Ｒ３）Ｒ４で表されるような、炭素数１６〜３０、好ましくは炭素数２０〜２８、より好ましくは炭素数２２〜２６の分枝アルキル基を有する（メタ）アクリレートが挙げられ、ここで、Ｒ３及びＲ４は、Ｒ２の炭素数が１６〜３０となる限りにおいて何ら制限はないが、Ｒ３としては、好ましくは炭素数６〜１２、より好ましくは炭素数１０〜１２の直鎖アルキル基、Ｒ４としては、好ましくは炭素数１０〜１６、より好ましくは炭素数１４〜１６の直鎖アルキル基である。
（Ｂ２）成分としては、より具体的には、２−デシル−テトラデシル（メタ）アクリレート、２−ドデシル−ヘキサデシル（メタ）アクリレート、２−デシル−テトラデシルオキシエチル（メタ）アクリレート等の炭素数２０〜３０の分枝状アルキル基を有する（メタ）アクリレートが挙げられる。
(B2) (Meth) acrylate having a branched alkyl group having 16 to 30 carbon atoms:
Examples of the component (B2) include branched hexadecyl (meth) acrylate, branched octadecyl (meth) acrylate, branched icosyl (meth) acrylate, branched docosyl (meth) acrylate, branched tetracosyl (meth) acrylate, Examples thereof include branched hexacosyl (meth) acrylate, branched octacosyl (meth) acrylate, and the like, and preferably represented by —C—C (R 3 ) R 4 , preferably have 16 to 30 carbon atoms, preferably 20 to 20 carbon atoms. 28, more preferably (meth) acrylate having a branched alkyl group having 22 to 26 carbon atoms, wherein R 3 and R 4 are not limited as long as R 2 has 16 to 30 carbon atoms. without, the R 3, preferably 6 to 12 carbon atoms, more preferably a linear alkyl group having 10 to 12 carbon atoms, and R 4 Is preferably 10 to 16 carbon atoms, more preferably a linear alkyl group having 14 to 16 carbon atoms.
More specifically, the component (B2) has 20 carbon atoms such as 2-decyl-tetradecyl (meth) acrylate, 2-dodecyl-hexadecyl (meth) acrylate, 2-decyl-tetradecyloxyethyl (meth) acrylate and the like. (Meth) acrylate having 30 branched alkyl groups.
（Ｂ）成分のポリ（メタ）アクリレートが、一般式（１’）で表されるモノマーの１種又は２種以上のモノマーと一般式（１’）で表されるモノマー以外のモノマーとの共重合体である場合の一般式（１’）で表されるモノマー以外のモノマーとしては、例えば、下記（Ｂａ）〜（Ｂｃ）に示すものが挙げられる。 The poly (meth) acrylate as the component (B) is a copolymer of one or more monomers represented by the general formula (1 ′) and a monomer other than the monomer represented by the general formula (1 ′). Examples of the monomer other than the monomer represented by the general formula (1 ′) in the case of a polymer include the following (Ba) to (Bc).
（Ｂａ）炭素数１〜４のアルキル基を有する（メタ）アクリレート：
（Ｂａ）成分としては、具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−又はｉ−プロピル（メタ）アクリレート、ｎ−、ｉ−又はｓｅｃ−ブチル（メタ）アクリレート等が挙げられ、メチル（メタ）アクリレートが好ましい。
(Ba) (Meth) acrylate having an alkyl group having 1 to 4 carbon atoms:
Specific examples of the (Ba) component include methyl (meth) acrylate, ethyl (meth) acrylate, n- or i-propyl (meth) acrylate, n-, i- or sec-butyl (meth) acrylate, and the like. And methyl (meth) acrylate is preferred.
（Ｂｂ）炭素数５〜１５のアルキル基又はアルケニル基を有する（メタ）アクリレート：
（Ｂｂ）成分としては、具体的には、オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、テトラデシル（メタ）アクリレート、ペンタデシル（メタ）アクリレート（これらは直鎖でも分枝状であってもよい）；オクテニル（メタ）アクリレート、ノネニル（メタ）アクリレート、デセニル（メタ）アクリレート、ウンデセニル（メタ）アクリレート、ドデセニル（メタ）アクリレート、トリデセニル（メタ）アクリレート、テトラデセニル（メタ）アクリレート、ペンタデセニル（メタ）アクリレート（これらは直鎖でも分枝状であってもよい）等が挙げられ、炭素数１２〜１５の直鎖アルキル基を主成分として有する（メタ）アクリレートが好ましい。
(Bb) (Meth) acrylate having an alkyl group or alkenyl group having 5 to 15 carbon atoms:
As the component (Bb), specifically, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl ( Meth) acrylate, pentadecyl (meth) acrylate (these may be linear or branched); octenyl (meth) acrylate, nonenyl (meth) acrylate, decenyl (meth) acrylate, undecenyl (meth) acrylate, dodecenyl (Meth) acrylate, tridecenyl (meth) acrylate, tetradecenyl (meth) acrylate, pentadecenyl (meth) acrylate (these may be linear or branched) and the like, and straight chain having 12 to 15 carbon atoms Archi Having a group as a main component (meth) acrylate.
（Ｂｃ）極性基含有モノマー；
（Ｂｃ）成分としては、アミド基含有ビニルモノマー、ニトロ基含有モノマー、１〜３級アミノ基含有ビニルモノマー、含窒素複素環含有ビニルモノマーおよびこれらの塩酸塩、硫酸塩、燐酸塩、低級アルキル（炭素数１〜８）モノカルボン酸塩、第４級アンモニウム塩基含有ビニルモノマー、酸素及び窒素を含有する両性ビニルモノマー、ニトリル基含有モノマー、脂肪族炭化水素系ビニルモノマー、脂環式炭化水素系ビニルモノマー、芳香族炭化水素系ビニルモノマー、ビニルエステル、ビニルエーテル、ビニルケトン類、エポキシ基含有ビニルモノマー、ハロゲン元素含有ビニルモノマー、不飽和ポリカルボン酸のエステル、ヒドロキシル基含有ビニルモノマー、ポリオキシアルキレン鎖含有ビニルモノマー、アニオン性基、燐酸基、スルホン酸基、又は硫酸エステル基含有イオン性基含有ビニルモノマー及びこれらの１価金属塩、２価金属塩、アミン塩若しくはアンモニウム塩等が挙げられる。
(Bc) polar group-containing monomer;
As the component (Bc), amide group-containing vinyl monomers, nitro group-containing monomers, primary to tertiary amino group-containing vinyl monomers, nitrogen-containing heterocyclic ring-containing vinyl monomers and their hydrochlorides, sulfates, phosphates, lower alkyls ( C1-C8) monocarboxylate, quaternary ammonium base-containing vinyl monomer, amphoteric vinyl monomer containing oxygen and nitrogen, nitrile group-containing monomer, aliphatic hydrocarbon vinyl monomer, alicyclic hydrocarbon vinyl Monomer, aromatic hydrocarbon vinyl monomer, vinyl ester, vinyl ether, vinyl ketones, epoxy group-containing vinyl monomer, halogen element-containing vinyl monomer, ester of unsaturated polycarboxylic acid, hydroxyl group-containing vinyl monomer, polyoxyalkylene chain-containing vinyl Monomer, anionic group, phosphate group, Sulfonic acid group, or a sulfuric ester group-containing ionic group-containing vinyl monomers and monovalent metal salts thereof, divalent metal salts, amine salts or ammonium salts.
（Ｂｃ）成分としては、具体的には、これらのうち、４−ジフェニルアミン（メタ）アクリルアミド、２−ジフェニルアミン（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリルアミド、ジエチルアミノエチル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、およびジエチルアミノエチル（メタ）アクリレート等の窒素含有モノマーが好ましい例として挙げられる。 Specific examples of the component (Bc) include 4-diphenylamine (meth) acrylamide, 2-diphenylamine (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, and dimethylaminopropyl. Preferred examples include nitrogen-containing monomers such as (meth) acrylamide, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate.
本発明における（Ｂ）成分において、一般式（１）で表される構造単位の構成比は、５モル％以上であることが好ましく、より好ましくは１５モル％以上であり、特に好ましくは３０モル％以上である。また、低温粘度特性の観点から、好ましくは８０モル％以下であり、より好ましくは６０モル％以下、特に好ましくは５０モル％以下である。より具体的には、上記（Ｂ１）、（Ｂ２）、（Ｂａ）、（Ｂｂ）及び（Ｂｃ）成分の構成比は、ポリ（メタ）アクリレートを構成するモノマー全量基準で、以下の通りであることが好ましい。 In the component (B) in the present invention, the constitutional ratio of the structural unit represented by the general formula (1) is preferably 5 mol% or more, more preferably 15 mol% or more, and particularly preferably 30 mol. % Or more. Moreover, from a viewpoint of a low-temperature viscosity characteristic, Preferably it is 80 mol% or less, More preferably, it is 60 mol% or less, Most preferably, it is 50 mol% or less. More specifically, the component ratios of the components (B1), (B2), (Ba), (Bb), and (Bc) are as follows based on the total amount of monomers constituting the poly (meth) acrylate. It is preferable.
（Ｂ１）成分：好ましくは５〜６０モル％、より好ましくは１０〜４０モル％、特に好ましくは２０〜４０モル％
（Ｂ２）成分：好ましくは５〜６０モル％、より好ましくは１０〜４０モル％、特に好ましくは１０〜３０モル％
（Ｂａ）成分：好ましくは０〜９０モル％、より好ましくは２０〜８０モル％、特に好ましくは３０〜７０モル％
（Ｂｂ）成分：好ましくは０〜６０モル％、より好ましくは５〜３０モル％、特に好ましくは１０〜２０モル％
（Ｂｃ）成分：好ましくは０〜２０モル％、より好ましくは０〜１０モル％、特に好ましくは１〜５モル％
Component (B1): preferably 5 to 60 mol%, more preferably 10 to 40 mol%, particularly preferably 20 to 40 mol%
Component (B2): preferably 5 to 60 mol%, more preferably 10 to 40 mol%, particularly preferably 10 to 30 mol%
Component (Ba): preferably 0 to 90 mol%, more preferably 20 to 80 mol%, particularly preferably 30 to 70 mol%
Component (Bb): preferably 0 to 60 mol%, more preferably 5 to 30 mol%, particularly preferably 10 to 20 mol%
Component (Bc): preferably 0 to 20 mol%, more preferably 0 to 10 mol%, particularly preferably 1 to 5 mol%
本発明における（Ｂ）成分の重量平均分子量は、特に制限はなく、通常５千〜１５万であるが、疲労寿命向上効果により優れる点で、好ましくは１万〜６万、より好ましくは１．５万〜３万、特に好ましくは１．５万〜２．４万である。
なお、ここでいう重量平均分子量は、ウォーターズ社製１５０−Ｃ ＡＬＣ／ＧＰＣ装置に東ソー社製のＧＭＨＨＲ−Ｍ（７．８ｍｍＩＤ×３０ｃｍ）のカラムを２本直列に使用し、溶媒としてはテトラヒドロフラン、温度２３℃、流速１ｍＬ／分、試料濃度１質量％、試料注入量７５μＬ、検出器示差屈折率計（ＲＩ）で測定したポリスチレン換算の重量平均分子量を意味する。
The weight average molecular weight of the component (B) in the present invention is not particularly limited and is usually from 5,000 to 150,000, but is preferably from 10,000 to 60,000, more preferably from the viewpoint of excellent fatigue life improvement effect. It is 50,000 to 30,000, particularly preferably 15,000 to 24,000.
In addition, the weight average molecular weight mentioned here uses two columns of Tosoh GMHHR-M (7.8 mm ID × 30 cm) in series on a Waters 150-C ALC / GPC apparatus, and the solvent is tetrahydrofuran, It means a weight average molecular weight in terms of polystyrene measured by a temperature of 23 ° C., a flow rate of 1 mL / min, a sample concentration of 1 mass%, a sample injection amount of 75 μL, and a detector differential refractometer (RI).
本発明の変速機用潤滑油組成物における（Ｂ）ポリ（メタ）アクリレート系添加剤の配合量は、組成物の１００℃における動粘度が３〜８ｍｍ２／ｓ、好ましくは４．５〜６ｍｍ２／ｓ、かつ、組成物の粘度指数が９５〜２００、好ましくは１２０〜１９０、より好ましくは１５０〜１８０となるような量であり、より具体的には、その配合量は、組成物全量基準で、希釈剤込みの配合量として、０．１〜１５質量％、好ましくは２〜１２質量％、特に好ましくは３〜８質量％である。（Ｂ）成分の配合量が上記範囲を超える場合、配合量に見合う疲労寿命向上効果が期待できないだけでなく、せん断安定性に劣り、初期の極圧性を長期間維持しにくいため好ましくない。 The blending amount of the (B) poly (meth) acrylate additive in the lubricating oil composition for transmission of the present invention is such that the kinematic viscosity at 100 ° C. of the composition is 3 to 8 mm 2 / s, preferably 4.5 to 6 mm. 2 / s, and the viscosity index of the composition is 95 to 200, preferably 120 to 190, more preferably 150 to 180. More specifically, the blending amount is the total amount of the composition. On the basis, the blending amount including the diluent is 0.1 to 15% by mass, preferably 2 to 12% by mass, and particularly preferably 3 to 8% by mass. When the blending amount of the component (B) exceeds the above range, not only the fatigue life improving effect corresponding to the blending amount cannot be expected, but also the shear stability is inferior and the initial extreme pressure property is difficult to maintain for a long period, which is not preferable.
本発明の変速機用潤滑油組成物には、その性能をさらに向上させる目的で、又は変速機用潤滑油に必要な性能を付与するために、必要に応じて、粘度指数向上剤、極圧剤、分散剤、金属系清浄剤、摩擦調整剤、酸化防止剤、腐食防止剤、防錆剤、抗乳化剤、金属不活性化剤、流動点降下剤、シール膨潤剤、消泡剤、着色剤等の各種添加剤を単独で又は数種類組み合わせて配合しても良い。 In order to further improve the performance of the lubricating oil composition for transmission of the present invention or to provide the necessary performance for the lubricating oil for transmission, a viscosity index improver, Agent, dispersant, metal detergent, friction modifier, antioxidant, corrosion inhibitor, rust inhibitor, demulsifier, metal deactivator, pour point depressant, seal swelling agent, antifoaming agent, colorant Various additives such as these may be blended alone or in combination.
粘度指数向上剤としては、公知の非分散型又は分散型ポリメタクリレート類（（Ｂ）成分を除く）、非分散型又は分散型エチレン−α−オレフィン共重合体又はその水素化物、ポリイソブチレン又はその水素化物、スチレン−ジエン水素化共重合体、スチレン−無水マレイン酸エステル共重合体及びポリアルキルスチレン等が挙げられる。
本発明の変速機用潤滑油組成物に粘度指数向上剤（（Ｂ）成分を除く）を配合する場合、その配合量は、組成物の１００℃における動粘度及び粘度指数の規定を満たす限り制限はなく、通常、組成物全量基準で０．１〜１５質量％、好ましくは０．５〜５質量％である。
Viscosity index improvers include known non-dispersed or dispersed polymethacrylates (excluding component (B)), non-dispersed or dispersed ethylene-α-olefin copolymers or hydrides thereof, polyisobutylene or the like. Examples thereof include hydride, styrene-diene hydrogenated copolymer, styrene-maleic anhydride ester copolymer, and polyalkylstyrene.
When blending a viscosity index improver (except for the component (B)) in the lubricating oil composition for transmission of the present invention, the blending amount is limited as long as the composition satisfies the stipulations of the kinematic viscosity and viscosity index at 100 ° C. Usually, it is 0.1 to 15% by mass, preferably 0.5 to 5% by mass based on the total amount of the composition.
極圧剤としては、亜リン酸、亜リン酸モノエステル類、亜リン酸ジエステル類、亜リン酸トリエステル類、及びこれらの塩から選ばれる少なくとも１種のリン系極圧剤、硫化油脂類、硫化オレフィン類、ジヒドロカルビルポリスルフィド類、ジチオカーバメート類、チアジアゾール類、及びベンゾチアゾール類から選ばれる少なくとも１種の硫黄系極圧剤、及び／又は、チオ亜リン酸、チオ亜リン酸モノエステル類、チオ亜リン酸ジエステル類、チオ亜リン酸トリエステル類、ジチオ亜リン酸、ジチオ亜リン酸モノエステル類、ジチオ亜リン酸ジエステル類、ジチオ亜リン酸トリエステル類、トリチオ亜リン酸、トリチオ亜リン酸モノエステル類、トリチオ亜リン酸ジエステル類、トリチオ亜リン酸トリエステル類、及びこれらの塩から選ばれる少なくとも１種のリン−硫黄系極圧剤からなる極圧剤を配合するのが好ましい。 Examples of extreme pressure agents include phosphorous acid, phosphorous acid monoesters, phosphorous acid diesters, phosphorous acid triesters, and salts thereof, and at least one phosphorus-based extreme pressure agent, sulfurized fats and oils , Sulfurized olefins, dihydrocarbyl polysulfides, dithiocarbamates, thiadiazoles, and benzothiazoles, and / or thiophosphorous acid, thiophosphorous acid monoesters Thiophosphite diesters, thiophosphite triesters, dithiophosphite, dithiophosphite monoesters, dithiophosphite diesters, dithiophosphite triesters, trithiophosphite, trithio Selected from phosphorous acid monoesters, trithiophosphite diesters, trithiophosphite triesters, and salts thereof Preferably blended the extreme pressure agent comprising a sulfur-based extreme pressure agent - at least one phosphorus that.
分散剤としては、炭素数４０〜４００の炭化水素基を有する、コハク酸イミド、ベンジルアミン、ポリアミン、及び／又はそのホウ素化合物誘導体等の無灰分散剤を配合することができる。
本発明においては、上記分散剤の中から任意に選ばれる１種類あるいは２種類以上の化合物を任意の量で含有させることができるが、通常、その含有量は、組成物全量基準で０．０１〜１５質量％、好ましくは０．１〜８質量％である。
As the dispersant, an ashless dispersant such as succinimide, benzylamine, polyamine, and / or a boron compound derivative thereof having a hydrocarbon group having 40 to 400 carbon atoms can be blended.
In the present invention, one or two or more compounds arbitrarily selected from the above dispersants can be contained in any amount, but the content is usually 0.01 based on the total amount of the composition. -15% by mass, preferably 0.1-8% by mass.
金属系清浄剤としては、アルカリ土類金属スルホネート、アルカリ土類金属フェネート、アルカリ土類金属サリシレート等の金属系清浄剤が挙げられる。
本発明においては、上記金属系清浄剤の中から任意に選ばれる１種類あるいは２種類以上の化合物を任意の量で含有させることができるが、通常、その含有量は、組成物全量基準で０．０１〜１０質量％、好ましくは０．１〜５質量％である。
Examples of the metal detergent include metal detergents such as alkaline earth metal sulfonate, alkaline earth metal phenate, and alkaline earth metal salicylate.
In the present invention, one or two or more compounds arbitrarily selected from the above metal-based detergents can be contained in any amount, but the content is usually 0 based on the total amount of the composition. 0.01 to 10% by mass, preferably 0.1 to 5% by mass.
摩擦調整剤としては、潤滑油用の摩擦調整剤として通常用いられる任意の化合物が使用可能であるが、炭素数６〜３０のアルキル基又はアルケニル基、特に炭素数６〜３０の直鎖アルキル基又は直鎖アルケニル基を分子中に少なくとも１個有する、アミン化合物、イミド化合物、脂肪酸エステル、脂肪酸アミド、脂肪酸金属塩等が好ましく用いられる。
本発明においては、上記摩擦調整剤の中から任意に選ばれる１種類あるいは２種類以上の化合物を任意の量で含有させることができるが、通常、その含有量は、組成物全量基準で０．０１〜５．０質量％、好ましくは０．０３〜３．０質量％である。
As the friction modifier, any compound usually used as a friction modifier for lubricating oils can be used, but an alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly a linear alkyl group having 6 to 30 carbon atoms. Alternatively, amine compounds, imide compounds, fatty acid esters, fatty acid amides, fatty acid metal salts, and the like having at least one linear alkenyl group in the molecule are preferably used.
In the present invention, one kind or two or more kinds of compounds arbitrarily selected from the above friction modifiers can be contained in any amount, but the content is usually 0.00 on the basis of the total amount of the composition. It is 01-5.0 mass%, Preferably it is 0.03-3.0 mass%.
酸化防止剤としては、フェノール系化合物やアミン系化合物等、潤滑油に一般的に使用されているものであれば使用可能である。
具体的には、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール等のアルキルフェノール類、メチレン−４，４−ビスフェノール（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール）等のビスフェノール類、フェニル−α−ナフチルアミン等のナフチルアミン類、ジアルキルジフェニルアミン類、ジ−２−エチルヘキシルジチオリン酸亜鉛等のジアルキルジチオリン酸亜鉛類、（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）脂肪酸（プロピオン酸等）あるいは（３−メチル−５−ｔｅｒｔブチル−４−ヒドロキシフェニル）脂肪酸（プロピオン酸等）と１価又は多価アルコール、例えばメタノール、オクタノール、オクタデカノール、１，６−ヘキサジオール、ネオペンチルグリコール、チオジエチレングリコール、トリエチレングリコール、ペンタエリスリトール等とのエステル等が挙げられる。
これらの中から任意に選ばれた１種類あるいは２種類以上の化合物は、任意の量を含有させることができるが、通常、その含有量は、潤滑油組成物全量基準で０．０１〜５質量％、好ましくは０．１〜３質量％であるのが望ましい。
As the antioxidant, any phenolic compound or amine compound that is generally used in lubricating oils can be used.
Specifically, alkylphenols such as 2,6-di-tert-butyl-4-methylphenol and bisphenols such as methylene-4,4-bisphenol (2,6-di-tert-butyl-4-methylphenol) , Naphthylamines such as phenyl-α-naphthylamine, dialkyldiphenylamines, zinc dialkyldithiophosphates such as zinc di-2-ethylhexyldithiophosphate, (3,5-di-tert-butyl-4-hydroxyphenyl) fatty acid ( Propionic acid etc.) or (3-methyl-5-tertbutyl-4-hydroxyphenyl) fatty acid (propionic acid etc.) and mono- or polyhydric alcohols such as methanol, octanol, octadecanol, 1,6-hexadiol, Neopentyl glycol, thiodiethylene glycol Triethylene glycol, esters of pentaerythritol and the like.
One or two or more compounds arbitrarily selected from these can be contained in any amount, but usually the content is 0.01 to 5 mass based on the total amount of the lubricating oil composition. %, Preferably 0.1 to 3% by mass.
腐食防止剤としては、例えば、ベンゾトリアゾール系、トリルトリアゾール系、チアジアゾール系、及びイミダゾール系化合物等が挙げられる。 Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
防錆剤としては、例えば、石油スルホネート、アルキルベンゼンスルホネート、ジノニルナフタレンスルホネート、アルケニルコハク酸エステル、及び多価アルコールエステル等が挙げられる。 Examples of the rust inhibitor include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
抗乳化剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、及びポリオキシエチレンアルキルナフチルエーテル等のポリアルキレングリコール系非イオン系界面活性剤等が挙げられる。 Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.
金属不活性化剤としては、例えば、イミダゾリン、ピリミジン誘導体、アルキルチアジアゾール、メルカプトベンゾチアゾール、ベンゾトリアゾール又はその誘導体、１，３，４−チアジアゾールポリスルフィド、１，３，４−チアジアゾリル−２，５−ビスジアルキルジチオカーバメート、２−（アルキルジチオ）ベンゾイミダゾール、及びβ−（ｏ−カルボキシベンジルチオ）プロピオンニトリル等が挙げられる。 Examples of metal deactivators include imidazoline, pyrimidine derivatives, alkylthiadiazoles, mercaptobenzothiazoles, benzotriazoles or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and β- (o-carboxybenzylthio) propiononitrile.
流動点降下剤としては、潤滑油基油に応じて公知の流動点降下剤を任意に選択することができるが、重量平均分子量が好ましくは２０，０００〜５００，０００、より好ましくは５０，０００〜３００，０００、特に好ましくは８０，０００〜２００，０００のポリメタクリレートが好ましい。 As the pour point depressant, a known pour point depressant can be arbitrarily selected according to the lubricating base oil, but the weight average molecular weight is preferably 20,000 to 500,000, more preferably 50,000. Polymethacrylates of ~ 300,000, particularly preferably 80,000 to 200,000 are preferred.
消泡剤としては、潤滑油用の消泡剤として通常用いられる任意の化合物が使用可能であり、例えば、ジメチルシリコーン、フルオロシリコーン等のシリコーン類が挙げられる。これらの中から任意に選ばれた１種類あるいは２種類以上の化合物を任意の量で配合することができる。 As the antifoaming agent, any compound usually used as an antifoaming agent for lubricating oil can be used, and examples thereof include silicones such as dimethyl silicone and fluorosilicone. One or two or more compounds arbitrarily selected from these can be blended in any amount.
シール膨潤剤としては、潤滑油用のシール膨潤剤として通常用いられる任意の化合物が使用可能であり、例えば、エステル系、硫黄系、芳香族系等のシール膨潤剤が挙げられる。 As the seal swelling agent, any compound usually used as a seal swelling agent for lubricating oil can be used, and examples thereof include ester-based, sulfur-based and aromatic-based seal swelling agents.
着色剤としては、通常用いられる任意の化合物が使用可能であり、また任意の量を配合することができるが、通常その配合量は、組成物全量基準で０．００１〜１．０質量％である。 As the colorant, any compound that is usually used can be used, and any amount can be blended. Usually, the blending amount is 0.001 to 1.0% by mass based on the total amount of the composition. is there.
これらの添加剤を本発明の変速機用潤滑油組成物に含有させる場合には、その含有量は組成物全量基準で、腐食防止剤、防錆剤、抗乳化剤ではそれぞれ０．００５〜５質量％、流動点降下剤、金属不活性化剤では０．００５〜２質量％、シール膨潤剤では０．０１〜５質量％、消泡剤では０．０００５〜１質量％の範囲で通常選ばれる。 When these additives are contained in the transmission lubricating oil composition of the present invention, the content is based on the total amount of the composition, and 0.005 to 5 mass for each of the corrosion inhibitor, rust inhibitor, and demulsifier. %, Pour point depressant, metal deactivator is 0.005 to 2% by mass, seal swelling agent is 0.01 to 5% by mass, and antifoaming agent is usually selected in the range of 0.0005 to 1% by mass. .
また、本発明の変速機用潤滑油組成物は、上記構成とすることで疲労寿命に優れた性能を付与することができるが、従来の自動変速機用、無段変速機用、手動変速機用潤滑油組成物に比べ攪拌抵抗低減による省燃費性能をより高めるために、組成物の１００℃における動粘度を８ｍｍ２／ｓ以下、好ましくは７ｍｍ２／ｓ以下、より好ましくは６．５ｍｍ２／ｓ以下、特に好ましくは６ｍｍ２／ｓ以下とすることが望ましい。また、４０℃における動粘度は、好ましくは４０ｍｍ２／ｓ以下、より好ましくは３５ｍｍ２／ｓ以下、特に好ましくは３０ｍｍ２／ｓ以下とすることが望ましい。また、自動変速機用、無段変速機用、手動変速機用潤滑油組成物としての極圧性をより高めるために、組成物の１００℃における動粘度を３ｍｍ２／ｓ以上とすること好ましく、４ｍｍ２／ｓ以上とすることがより好ましく、５ｍｍ２／ｓ以上とすることが特に好ましく、組成物の４０℃における動粘度を好ましくは１５ｍｍ２／ｓ以上、より好ましくは２０ｍｍ２／ｓ以上、特に好ましくは２５ｍｍ２／ｓ以上とすることが望ましい。 In addition, the lubricating oil composition for a transmission according to the present invention can provide performance with excellent fatigue life by adopting the above-described configuration. However, the conventional lubricating transmission composition, continuously variable transmission, manual transmission In order to further improve the fuel saving performance by reducing the stirring resistance compared to the lubricating oil composition for use, the kinematic viscosity at 100 ° C. of the composition is 8 mm 2 / s or less, preferably 7 mm 2 / s or less, more preferably 6.5 mm 2. / S or less, particularly preferably 6 mm 2 / s or less. The kinematic viscosity at 40 ° C. is preferably 40 mm 2 / s or less, more preferably 35 mm 2 / s or less, and particularly preferably 30 mm 2 / s or less. Further, in order to further enhance the extreme pressure properties as a lubricating oil composition for automatic transmissions, continuously variable transmissions, and manual transmissions, the kinematic viscosity at 100 ° C. of the composition is preferably 3 mm 2 / s or more, It is more preferably 4 mm 2 / s or more, particularly preferably 5 mm 2 / s or more, and the kinematic viscosity at 40 ° C. of the composition is preferably 15 mm 2 / s or more, more preferably 20 mm 2 / s or more, It is particularly preferable that the thickness is 25 mm 2 / s or more.
本発明の変速機用潤滑油組成物は、従来品を低粘度化しても疲労寿命に優れ、潤滑油起因の攪拌抵抗を低減できるため、例えば自動車用変速機用、特に自動変速機用、無段変速機用又は手動変速機用あるいは自動車用終減速機用、として使用することで自動車の燃費の向上に寄与することが可能となる。 The lubricating oil composition for a transmission of the present invention has an excellent fatigue life even when the viscosity of a conventional product is reduced, and can reduce the agitation resistance caused by the lubricating oil. For example, for a transmission for an automobile, particularly for an automatic transmission, By using it for a step transmission, a manual transmission, or an automobile final reduction gear, it becomes possible to contribute to an improvement in the fuel consumption of the automobile.
本発明の変速機用潤滑油組成物は、低粘度であっても疲労寿命が長く、特に自動車用の自動変速機、手動変速機、無段変速機等歯車や軸受け等の十分な耐久性を兼ね備え、自動車の省燃費化を達成しうる。 The lubricating oil composition for a transmission according to the present invention has a long fatigue life even if it has a low viscosity. In particular, it has sufficient durability such as gears and bearings for automobile automatic transmissions, manual transmissions, continuously variable transmissions, and the like. At the same time, it can achieve fuel savings for automobiles.
以下、本発明の内容を実施例及び比較例によってさらに具体的に説明するが、本発明はこれらに何ら限定されるものではない。 Hereinafter, the content of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these.
（実施例１〜７、比較例１〜３）
表１に示す組成に従い、本発明に係る変速機用潤滑油組成物（実施例１〜７）を調製した。これらの組成物につき、以下に示す性能評価試験を行い、その結果も表１に示した。
また、表１に示す組成に従い、比較のための変速機用潤滑油組成物（比較例１〜３）を調製し、これらの組成物についても同様の性能評価試験を行い、その結果も表１に示した。
(Examples 1-7, Comparative Examples 1-3)
According to the compositions shown in Table 1, transmission lubricating oil compositions (Examples 1 to 7) according to the present invention were prepared. These compositions were subjected to the following performance evaluation tests, and the results are also shown in Table 1.
Moreover, according to the composition shown in Table 1, the lubricating oil composition for transmissions for comparison (Comparative Examples 1 to 3) was prepared, and the same performance evaluation test was conducted for these compositions. It was shown to.
［疲労寿命試験］
ＩＰ３００／８２「Rolling Contact Fatigue Test For Fluid in a Modified Four-Ball Machine」に準拠した「Four-Ball Extreme-Pressure Lubricant Testing Machine」を用い、「７．Procedure B」の試験条件を以下に変更して疲労寿命を測定した。
（試験条件）
回転数 ： ３０００ｒｐｍ
油温 ： １２０℃
面圧 ： ３．９ＧＰａ
（判断基準）
試験鋼球にピッチングが発生するまでの時間を疲労寿命とし、３回の試験の結果からＬ５０（平均値）を計算した。
[Fatigue life test]
Using “Four-Ball Extreme-Pressure Lubricant Testing Machine” compliant with IP300 / 82 “Rolling Contact Fatigue Test For Fluid in a Modified Four-Ball Machine”, the test conditions of “7. Procedure B” were changed to the following: The fatigue life was measured.
(Test conditions)
Rotation speed: 3000rpm
Oil temperature: 120 ° C
Surface pressure: 3.9 GPa
(Judgment criteria)
L50 (average value) was calculated from the results of three tests, assuming that the time until pitching occurred in the test steel ball was the fatigue life.
［低温粘度測定］
ＪＰＩ−５Ｓ−２６−８５に規定する「ギヤ油の低温粘度試験方法」に準拠し、液浴低温槽にて変速機用潤滑油組成物の−４０℃における低温粘度を測定した。本発明においては、２０，０００ｍＰａ・ｓ以下であることが好ましく、疲労寿命に優れる点で１０，０００ｍＰａ・ｓ以上であることが望ましい。
[Low temperature viscosity measurement]
The low temperature viscosity at −40 ° C. of the lubricating oil composition for transmissions was measured in a liquid bath low temperature bath in accordance with “Gear oil low temperature viscosity test method” defined in JPI-5S-26-85. In this invention, it is preferable that it is 20,000 mPa * s or less, and it is desirable that it is 10,000 mPa * s or more from the point which is excellent in a fatigue life.
表１に示したとおり、本発明における（Ｂ）成分を使用した本発明にかかる変速機用潤滑油組成物（実施例１〜７）は、低粘度であっても疲労寿命に優れることがわかる。特に（Ｂ）成分として重量平均分子量が１．５〜２．４万のポリメタアクリレート系添加剤を配合した場合に疲労寿命により優れ（実施例１と実施例６、実施例４と実施例７の比較）、さらに、（Ａ２）成分として（Ａ２ｂ）成分を併用した場合に特に疲労寿命が向上することがわかる（実施例４と実施例１〜３及び５、実施例７と実施例６との比較）。
一方、本発明における（Ｂ）成分の代わりに、炭素数１６以上のメタアクリレートを構造単位として実質的に含まないポリメタアクリレート系添加剤を使用した場合（比較例１〜３）、いずれも疲労寿命に劣ることがわかる（実施例１、実施例６との比較）。
As shown in Table 1, it can be seen that the lubricating oil compositions for transmissions according to the present invention using the component (B) in the present invention (Examples 1 to 7) are excellent in fatigue life even when the viscosity is low. . In particular, when a polymethacrylate-based additive having a weight average molecular weight of 1.5 to 24,000 is blended as the component (B), the fatigue life is excellent (Examples 1 and 6, Example 4 and Example 7). In addition, it can be seen that the fatigue life is particularly improved when the component (A2b) is used in combination as the component (A2) (Example 4 and Examples 1 to 3 and 5, Example 7 and Example 6). comparison).
On the other hand, when a polymethacrylate-based additive that does not substantially contain a methacrylate having 16 or more carbon atoms as a structural unit is used instead of the component (B) in the present invention (Comparative Examples 1 to 3), both are fatigued. It turns out that it is inferior to a lifetime (comparison with Example 1 and Example 6).
Claims (1)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
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| JP2004308828A JP4907074B2 (en) | 2004-10-22 | 2004-10-22 | Lubricating oil composition for transmission |
| EP05799398A EP1808476B1 (en) | 2004-10-22 | 2005-10-19 | Lubricant composition for transmission |
| AT05799398T ATE514766T1 (en) | 2004-10-22 | 2005-10-19 | LUBRICANT COMPOSITION FOR TRANSMISSIONS |
| CN200580040294XA CN101065469B (en) | 2004-10-22 | 2005-10-19 | Lubricating oil composition for transmission |
| PCT/JP2005/019644 WO2006043709A1 (en) | 2004-10-22 | 2005-10-19 | Lubricant composition for transmission |
| KR1020077010980A KR101347964B1 (en) | 2004-10-22 | 2005-10-19 | Lubricant composition for transmission |
| US11/737,339 US8846589B2 (en) | 2004-10-22 | 2007-04-19 | Lubricating oil composition for transmission |
| US13/103,582 US20120065109A1 (en) | 2004-10-22 | 2011-05-09 | Lubricating oil composition for transmission |
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| JP2004308828A JP4907074B2 (en) | 2004-10-22 | 2004-10-22 | Lubricating oil composition for transmission |
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| JP4907074B2 true JP4907074B2 (en) | 2012-03-28 |
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| JP5311748B2 (en) * | 2007-02-26 | 2013-10-09 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition |
| CN101652460A (en) | 2007-03-30 | 2010-02-17 | 新日本石油株式会社 | Lubricant base oil, method for production thereof, and lubricant oil composition |
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| JP2009155639A (en) * | 2007-12-05 | 2009-07-16 | Nippon Oil Corp | Lubricant composition |
| JP5483662B2 (en) | 2008-01-15 | 2014-05-07 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition |
| CN101945983A (en) * | 2008-02-13 | 2011-01-12 | 出光兴产株式会社 | Lubricating oil composition for continuously variable transmission |
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| JP5345808B2 (en) * | 2008-07-25 | 2013-11-20 | Ｊｘ日鉱日石エネルギー株式会社 | Engine oil composition |
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| US20040176256A1 (en) * | 2002-11-07 | 2004-09-09 | Nippon Oil Corporation | Lubricating oil composition for transmissions |
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| JP3949069B2 (en) * | 2003-02-21 | 2007-07-25 | 新日本石油株式会社 | Lubricating oil composition for transmission |
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| JP4536370B2 (en) * | 2003-12-26 | 2010-09-01 | 三洋化成工業株式会社 | Lubricating oil composition |
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